Condensation products of aromatic hydrocarbons and symmetrical dichloroacetone and process for producing same



Patented May 1, 1951 CONDENSATION PRODUCTS OF AROMATIC HYDROCARBONS -ANDSYMMETRICAL DI- CHLOROACETONE AND PROCESS FOR PRODUCING SAME John 'l.Pinkston, Jr., Euclid, Ohio, assignor to Universal Oil Products Company,Chicago, 111.. a corporation of Delaware No Drawing. Application August3, 1946, Serial No. 688,339

I 9 Claims. 1 lhis application is a continuation-in-part of myco-pending application Serial No. 489,807, filed June 5, 1943. 4 I Thisinvention relates to a process for preparing resins by interactingaromatic hydrocarbons and at least one member of the group consisting ofa,a-dihalo ketones and alkylene dihalides in the presence of aFriedel-Crafts metal halide catalyst,

An object of this invention is to form a resin suitable forincorporating into surface coating materials by reacting aromaticcompounds having at least two replaceable nuclear hydrogen atoms permolecule with a dihalogenated organic compound selected from the membersof the group consisting of a,a-dihalo ketones and. alkylene dihalides.

Another object of this invention is to form a resin by condensing anaromatic hydrocarbon having at least two replaceable nuclear hydrogenatoms per molecule with a dihalogenated organic compound selected fromthe group consisting of a,a'-dlha10 ketones and alkylene dihalides.

Still another object of this invention is to form a resin by condensinga benzene hydrocarbon having two replaceable nuclear hydrogen atoms withsymmetrical dichloroacetone in the presence of a Friedel-Crafts halidecatalyst.

A further object of this invention is a resinous composition formed byreacting a dialkyl benzene hydrocarbon, a symmetrical dihalo ketone andan alkylene dihalide in the presence of a Friedel- Crafts halidecatalyst.

One specific embodiment of my invention relates to a process forproducing resins which comprises condensing an aromatic hydrocarbonhaving at least two replaceable nuclear hydrogen atoms, an ld-symmetrical dihaloketone, and an alkylene dihalide in the presence ofa Friedel Crafts halide catalyst.

.Another embodiment of my invention relates to afprocess for producing aresin which comprises reacting an aromatic hydrocarbon containing atleast two replaceable hydrogen atoms with a symmetrical dichloro ketonein the presence of a Friedel-Crafts metal chloride catalyst.

4 A further embodiment of my invention comprises a resinous productformed by reacting a condensible benzene hydrocarbon, a symmetricaldihalo ketone and an alkylene dihalide in the presence of aFriedel-Crafts metal halide catalyst.

The preparation of high molecular weight organic material, varying inproperties from viscous oils to resinous solids, by thecondensation ofaromatic hydrocarbons and alkylene dihalides,

such as ethylene dichloride, has been known for some time. I have foundthat a new resinous material, having a softening point above 200 F. (933C.) and suitable for incorporation into surface coating materials may beprepared by reacting aromatic hydrocarbons having two replaceablehydrogen atoms with symmetrical dihalogenated ketones in the presence ofa Friedel- Crafts metal halide catalyst.

Other related resinous compositions are also obtained by applying myprocess to the condensation of condensible aromatic hydrocarbons,dihalogenated ketones, and alkylene dihalides in the presence of aFriedel-Crafts metal halide catalyst. The resultant high molecularweight polyketone resins may be used as such in the preparation ofcoating materials and varnishes or they may be modified further byreaction with polyamines or with aliphatic aldehydes such as, forexample, formaldehyde, acetaldehyde, crotonaldehyde, and the like, oralkyl ketones in the presence of a condensation catalyst whereby crosslinkages may be formed between molecules of high molecular weightpolyketone with a re sultant increase in the molecular weight andsoftening point of the resultant product,

Aromatic hydrocarbons used in my process may be either pure aromatichydrocarbons, aromaticcontaining hydrocarbon fractions, certainsubstituted aromatic hydrocarbons, or mixtures of these. 'Thehydrocarbon fractions suitable for use in the process may be thosewithin the gasoline boiling range, the boiling range of kerosene orother heavier hydrocarbon stocks. For use in my process the aromatichydrocarbon must contain at least two replaceable hydrogen atoms. Sucharomatic hydrocarbons thus include benzene, toluene, xylenes,ethylbenzene, diethylben' zone, and more highly alkylated benzene hydrocarbons having not more than 4 alkyl groups per molecule. and otherpolycyclic aromatic hydrocarbons having at least two replaceable nuclearhydrogen atoms are also utilizable in this process. The alkylsubstituents of these various alkylated berm length often undergoscission during the process and the olefinic hydrocarbons which areformed from the alkyl groups so split oif from thesalkyl aromatichydrocarbon undergo polymerization reactions. The aromatic compoundsutilizable in my process may also contain nuclear halogen substituents,particularly fluorine, chlorine, or-

Naphthalene, alkylated naphthalenes the organic layer.

bromine. Thus monochlorobenzene may be used or dichlorobenzene, orchlorotoluene, fluoroxylenes, and the like.

All of-the difierent aromatic compounds which may be employed in myprocess will not give equivalent results. Thus, aromatic hydrocarbonshaving only two replaceable nuclear hydrogen atoms react with alkylenedihalides and symmetrical dihalo ketones to form :resins with a linearstructure while other aromatic hydrocarbons'containing three or fourreplaceable nuclear hydrogen atoms react with .alkylene 'clihalides andsymmetrical dihalo ketones to form a crosslinked resinous material.

Symmetrical dihalo acetone, particularly masymmetrical dichloroa-cetone,is'the dihaloketone preferred for use in my process for producingresins, but other a,a-dihalogen substituted'ketones may be usedsimilarly. These different q,a'-symmetrical dihalogenated ketonesmay berepresented by the formula:

R1 R3 X 3o- JX it t .Ri

wherein each 'ofR R R. and R 'represents a member of the groupconsisting-of hydrogen, an alkyl radical, a cycloalkyl radical, andan'aralkyl H H Ri ht-R 3;.

wherein each of R and R represents a'member ='of the group consisting ofa hydrogen atom, an "alkyl-radical, a cycloalkyl radical and an aralkylradical, and X and X each represents halogen,

generally chlorine.

"Ih'e Friedel-Crafts halide catalysts used in my condensation processinclude particularly metal "halides, such as aluminium chloride,aluminum radical, and X and X represent halogensypar- T bromide, bismuthchloride, ferric chloride, zinc I chloride, stannic chloride, mercuricchloride, etc.

These catalysts may also be used in mixtures with one another or with asolvent such as a nitroparaffin, a low boiling paraffinic hydrocarbon,etc.

Sometimes it is convenient to deposit the active catalyst upon asupporting or carrying material,

such .as crushed porcelain, pumice, fire-brick, silica, diatomaceousearth, alumina, activated carbon, etc., and then use the supportedcatalyst .in granular form as areactor packing material.

In carrying out my process an aromatic hydrocarbon of the type hereinset forth is reacted with .an a,a'-di-.haloketone at a temperature andfor .a time sufiicient to form a product which, when decomposed with.water .and separated from the unreacted starting material, is a softplastic substance. The temperature used in effecting this reaction isfrom about to about 115 C. and is preferably about 100 C. .After thearomatic "hydrocarbon and haloketone are so reacted, the resultantreacted mixture is decomposed with water and the aqueous layer isseparated from The unreacted symmetrical dihaloketone is removed, forexample, by extraction with asolvent,as acetone, and the plastic plasticresidue of .resin-like material.

4 residue is heated to a temperature of from about 200 to about 300 C.to drive ofi water. The resultant product upon cooling, sets quickly toa hard, clear, resin.

I have found that this first step of the reaction must be carefullycontrolled in order to avoid charring in the last step of the process.Completion of the first reaction step is indicated by an increasein theviscosity of the reaction mixture accompanied by a slight swelling. Ifthe condensation reaction is continued beyond this point, the product,after hydrolysis and separation from unreacted material, is a hard,brittle,

-opaque,'and slightly soluble resin which chars on heating. If theprimary reaction is stopped before :the indicated point, the productafter hydrolysis is a viscous liquid which may be converted, however, toa resinous material by further 3 heating.

tioned herein may be admixed with the dihaloiketcne'such assymmetricaldichloroacetone. By

using such'a combination of reactants, resins may be'formed havingproperties intermediate between those formed by employing either onlythe alkylene dihalide or the dihaloketone with the aromatic hydrocarbon.Resins formed by combining the three reactants, that is aromatichydrocarbon, dihaloketonaand alkylene dihalide aremore soluble inorganic solvents, have better adherence to glass and metal surfaces andimproved flexibility over those formedby reacting thearomatichydrocarbonwith only one type of the dihalo compounds, as well as betterwaterresistance than thoseformed from the dihaloketones and: aromatichydrocarbons alone.

Also itheseresinsmay be made byreacting the aromatic compound with fromabout 1 to about 5 molecular proportions of dihalo-compounds selectedfrom the group consisting of dihaloketones and alkylene dihalides, atleast '10 per cent of said dihalo-compounds'being dihaloketones. The

use of the ketonic component in the production 'c'f the resins has theadvantage that the resultant chloride, petroleum fractions, such aspetroleum naphthas, and also natural drying oils such as linseed oil,and synthetic drying oils.

The following examples are given to illustrate results of my processalthough'these illustrations are given with'no intention of restrictingunduly the broad scope of the invention.

Example I 23.8 parts by weight of 'a mixture of 'xylenes containing'ortho, meta, and para xylenes, 1.8.9

parts by weight of aluminum chloride "and 57.1

parts by weight of symmetrical dichloroacetone were heated in arotatable steel autoclave at'about C. for nine hours. The resultantreaction mixture was decomposed with water and separated into unreac'tedstarting materials and a This plasticresidue was heated untilfro'thingceased'and a clear, hardres'inous product was obtained with a meltingpoint of 99 C. by the ball and ring method.

Example II Another reaction mixture, comprising one molecular proportionof mixed xylenes, 0.5 molecular proportion of symmetricaldichloroacetone and 0.5 molecular proportion of ethylene dichloride inthe presence of aluminum chloride catalyst at about 99 C. yields aplastic material which after further heating is converted into a hard.resinous product of somewhat lighter color than that described inExample I.

The nature of the present invention and its utility are evident from thepreceding specification and examples, although neither section isintroduced to limit unduly the generally broad scope of the invention.

I claim as my invention:

1. A process for producing resins which comprises reacting a xylene, analkylene dichloride, and symmetrical dichloroacetone at a temperature offrom about 60 C. to about 115 C. and in the presence of a Friedel-Craftsmetal halide catalyst.

2. A process for preparing resins which comprises reacting a Xylene,ethylene dichloride, and symmetrical dichloroacetone in the presence ofaluminum chloride and at a temperature of from about 60 C. to about 115C.

3. A process for preparing resins which comprises reacting xylene withsymmetrical dichloroacetone in the presence of aluminum chloride and ata temperature of from about 60 C. to about 115 C.

4. A process for producing resins which comprises reacting a xylene withsymmetrical dichloroacetone at a temperature of from about 60 C. toabout 115 C. and in the presence of a Friedel-Crafts metal halidecatalyst;

5. A composition of matter comprising the condensation product of aXylene and symmetrical dichloroacetone, said product being a 6 hard,clear resin having a softening point above about 200 F.

6. A proces for producing resins which comprises reacting an aromatichydrocarbon having at least two replaceable nuclear hydrogen atoms withsymmetrical dichloroacetone at a temperature of from about 60 C. toabout 115 C. and in the presence of a Friedel-Crafts metal halidecatalyst.

7. A composition of matter comprising the condensation product of anaromatic hydrocar bon having at least two replaceable nuclear hydrogenatoms and symmetrical dichloroacetone, said product being a hard, clearresin having a softening point above about 200 F.

8. A proces for producing resins which comprises reacting an aromatichydrocarbon having at least two replaceable nuclear hydrogen atoms,symmetrical dichloroacetone and ethylene dichloride at a temperature offrom about 60 C. to about 115 C. and in the presence of a Friedel-Crafts metal halide catalyst.

9. A composition of matter comprising the condensation product of anaromatic hydrocarbon having at least two replaceable nuclear hydrogenatoms, symmetrical dichloroacetone and ethylene dichloride.

JOHN T. PINKSTON, JR.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,235,860 Williams Mar. 25, 19412,238,638 Gleason Apr. 15, 1941 2,323,898 DAlelio July 13, 1943 OTHERREFERENCES Fuson: Jour. Amer. Chem. Soc., vol. 60, pages 2935-2936(1938).

5. A COMPOSITION OF MATTER COMPRISING THE CONDENSATION PRODUCT OF AXYLENE AND SYMMETRICAL DICHLOROACETONE, SAID PRODUCT BEING A HARD, CLEARRESIN HAVING A SOFTENING POINT ABOVE ABOUT 200* F.